Heavy metal complex compounds of ortho-hydroxy-azo-perimidine dyestuffs



Patented Feb. 11, 1930 UNITED STATES PATENT OFFICE wmrnrn HENTBICH AND LUDWIG ZEH, or wrnsnonr-on-rnngnnmn, GERMANY, AS-

SIGNORS 'ro GENERAL ANILINE wonxs, me, on NEW YORK, N. Y., A. CORPORATION OF DELAWARE HEAVY METAL COM ZPLEX COMPOUNDS 0! ORTHO-HYDROXY-AZO-PERIMIDINE DYESTUFFS No Drawing. Original application filed. February 25, 1927, Serial No. 171,070,.and in Germany March -1, 1926. Divided and this application filed October 18, 1927. Serial No. 227,053.

In our copending application Ser. No. 171,070 we have described new acid azo-dyestuffs which are produced if the ortho-hydroxyazo-dyestufi's, obtained through coupling of ortho hydroxydiazo compounds with 1.8-naphthylenediamine or its derivatives are transformed, in the usual manner, into perimidines or their substitution products or derivatives. The analogous new ortho-hydroxydiazoperimidine-dyestuffs can also be obtained if perimidines suitable for the coupling, or their substitution products or derivatives, are coupled with ortho-hydroxydiazo compounds.

We have found that the azo-dyestuffs, obtained through either of the above mentioned processes through the influence of metal-segwherein X represents hydrogen No SO ,H, Cl, -COOH or alkyl, represents hydrogen or an alkali-metal, Me represents a heavy metal, y represents 1 or %and Z represents a peri-substituent:

regating media, absorb metals, particularly chromium and copper, thus thereby effecting the production of tinctorially strong metal complex compounds which are I especially adapted for use in dyeing animal fibres. The colorings produced in a neutral oracid bath on the fiber by the use of these metal complex compounds are distinguished by evenness and a pronounced fastness to washing, fulling, perspiration, carbonizing and li ht. If the -ortho-hydroiry-azo-perimidineyestuifs, which have been deposited upon animal fiber, are treated with metal-segregating media, during or after the process of coloring, very fast shades having similar properties are obtained.

Example 1. The diazo compound of 234 parts by weight of 6-nitro-2-amino-1-hydroxybenzolr-sulfonic acid is dissolved in an aqueous solution of 238 parts by weight of 1 8 naphthylenediamino 4 sulfonic acid.

Through gradual addition of sodium acetate solution the Kongo-acid reaction of the reaction mixture is slowly dulled. When the coupling is finished, the dyestufi' so formed is separated, in the customary manner, from the reaction liquid and then redissolved in cold water with the addition of sodium hydroxide. Phosgene is introduced under stirring at 40 (1., taking care to maintain the solution weakly alkaline. When'this opera probably the formula of 4.6-dinitro-2-amino-1-hydroxybenzol, and otherwise treated in the same manner, a dyest-ufi is obtained "which dyes wool, in an acid bath, a reddish-brown shade. After chroming changes the shade to green. The chromated dyeing is very even and of good fastness to falling, perspiration and light.

If, in place of phosgenating the product from 4.6 dinitro 2 amino 1 hydroxybenzol and 1.S-naphthylene-diamine-4-sulfonic acid, the said product is treated at about 30 C., under very good stirring, with thiophosgene (CSCL in the presence of acid-binding tion is finished, the thus obtained dihydroperimidone derivative (nomenclature according to Sachs, Ann. 365, 67, 1909) having most SOaNa (4) OJNA or, respectively: the 2-hydroxyperimidinedellvatlvei media, a dihydrothioperimidone (*2) -de- 011 rivative, or respectively a 2-mercaptoperimi- SO;Na(4) dine-derivative, having most probably the o,1-I- 1 2 N=NC1oH|-NH 1 formula: Y

5 3 N= -o11 H' 4 (8) some 4 o,N- 1 2 N=NC1oHr-NH 1 5 3 n- =s is freed of salt, filtered and washed. 4 (8) The above described dyestufi is soluble in NO concentrated sulfuric acid with a bluishgreelf color, soluble in water with a bluishred color, and yields, on careful reduction with stannous chloride and hydrochloric some 4 acid, 2.6-diamino-1-11ydroxy-benzol-4-su1- 1 fonic acid and amino-sulfo-dihydro-perimi- 6 2 done. 5 4 3 (8) The same dyestuff can be obtained, if, instead of causing the reaction of the dyestufi N0: 1

. from 6 nitro 2 amino 1 hydroxybenzol 4- even, greenish-blue shade of good fastness is obtained, which has similar dyeing properties as the above mentioned dihydroperimidone-derivatives.

The above described phosgenated or-thiophosgenated compounds are soluble in water with a brown to bluish-red color. Careful sulfonic acid and 1.S-naphthylenc-diamilie-4- sulfonic acid with phosgene, one treats the said dyestutf with potassium-cyanate in an acid solution.

The dyestufi so produced dyes wool, in an acid bath Bordeaux-red; when chromated, the shade changes into a clear greenish-blue fast to falling, perspiration, carbonizing,

chloric acid yields 2.4.6-triamino-l-hydroxyand light. The coppered colorlng on the fiber benzol and amino-sulfo-dihydro-peri1nidoneis a beautiful blue; the coloring, produced in o i lf -di1 d -t} i i id the bath in the presence of saltsof copper, is ti l gf' of (luahtles- The copper-containing products, obtained U PP contamlng 001111318X P p from the said phosgenated or thiophosgenat- 3 has been i f t 2 ed dyestuffs respectively through treatment a ove process um er warm rea men WI 1 x 1 a salts of copper, dyes wool in an acid bath a g izg g jfisgggifiiz beautiful lmw'blm shade which with a hindsomc loss which d 4 shin )ers Jll'tltlOll fullin and i a Wings P035888 1? fast 9 YET F v i l f very good fastness properties, as for example:

ighttpobebebilpg {one fastness to fullin perspiration and li ht. cial light. lhe chromlulu-containing com- T1 d f l d plex compound, dyed upon wool, yields an are z fg i ggf z g i% gg i gisfgi i and in concentrated sulfuric acid with a greenish-blue color.

E wample 3.-The diazo-c mpound, produced in the usual manner from 224 parts by weight of 6-nitro-2-aminc-1-hydroxy-benzol--sulfonic acid is coup-ed, in acetic acid solution, with 318 parts by weight of the reaction product from 1 mol. of cyclohexanone and 1 mol. of 1.8-naphthylene-diamino-4-su1- pro )erties.

Tie copper and chromium compounds above. described are. soluble in water with a reddish-blue c010 and in concentrated sulfuric acid with a bluish-green color.

[fa-ample ..lf. for the diam-compound of (3 nitro -2 --amino- 1 -li droxybenzol -4-sultonic acid in Example 1, there is substituted the diazo compound of 199 parts by weight reduction with stannous chloride and hydrofonic acid,having most probably the formula and which is obtained through condensation of the said components in a weak, mineralacid solution at water-bath temperature. The dyestufi so produced, having most probably the formula:

A s OaNa 4 onhon/ treated with copper sulfate at raised tem- *acid bath deep Bordeaux.- Through afterchromating the shade changes into an olive of good fastness qualities.

The same dyestuff may be obtained by cou-' pling the above mentioned diazo compound with 1.8 naphthylene diamino 4: sulfonic acid, isolating the resulting azo-compound, and condensing the thus isolated product,

' in aqueous solution, with acetone in a Weak mineral-acid medium in the warm.

If, in the above example, the diazo compound of 6-chlorol-nitro-2-amino-1-hydroxybenzol is replaced by the diazo compound of 4.6-dinitro-2-amino-1-hydroXybenzol and the succeeding operations conducted according to either of the two above described processes, a dyestuif is obtained as the final product which dyes wool, in an acid bath, a reddish dark brown shade. Through coppering' afterwards, the shade is changed into a beautiful, fast blue-black. A similar, somewhat greener, shade is obtained by dyeing wool, in an acid bath, in the presence of copper salts. I

This is a division of our application Ser. No. 171,070.

We claim:

1. As new products heavy metal complex compounds of ortho-hydroXy-azo-perimidine dyestuffs having most probably the general formula:

wherein X represents hydrogen, NO

sents hydrogen or a metal, Me represents a OH Z stannous chloride and hydrochloric acid 2.4.6

triamino-l-hydroxy-benzol and amino-sulfodihydro-perimidone-(-2), and dyeing wool in an acid bath even glossy deep black shades fast to washing, fulling, perspiration, carbonizing and light.

In testimony whereof We have hereunto set our hands.

WINFRID HENTRICH. LUQWIG ZEH.

wherein X represents hydrogen, NO

SO H, Cl, -COOH or alkyl, M represents hydrogen or an alkali metal, Me represents a heavy metal of the group comprising chromium and copper, 7/ represents 1 or 2 and Z represents a peri-substituent:

1:1 ll. l1, lil

said dyestufis being, when dried and ground, generally dark, metallic, lustrous powders soluble in concentrated sulfuric acid and in water, and dyeing wool in an acid bath shades fast to washing, fulling, perspiration, carbonizing and light.

3. As a new product the copper compound of the ortho-hydroxy-azo-perimidine dyestuff having most probably the formula:

wherein M represents hydrogen or an alkali metal, and Z represents the peri-substituent:

said dyestufi being, when dried and ground a dark,-metallic lustrous powder, soluble in water with a bluish-black color, soluble in concentrated sulfuric acid with a greenishblue color, yielding on careful reduction with 

